CN100491282C - Preparation method of high-performance dehydragent for graft copolymerization for carboxylate - Google Patents
Preparation method of high-performance dehydragent for graft copolymerization for carboxylate Download PDFInfo
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- CN100491282C CN100491282C CNB2007100987954A CN200710098795A CN100491282C CN 100491282 C CN100491282 C CN 100491282C CN B2007100987954 A CNB2007100987954 A CN B2007100987954A CN 200710098795 A CN200710098795 A CN 200710098795A CN 100491282 C CN100491282 C CN 100491282C
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a preparing method of graft copolymerization carboxylate high-performance dehydragent belonging to dehydragent domain, which comprises the following steps: choosing methoxy carbowax with molecular weight distributing between 1000-2000 and acroleic acid or methacrylic acid as main raw material; adopting total acid method esterified priority method; preparing intermediate (big monomer) with polymerization activity; adding third monomer into polymerization reaction; adjusting polymerization activity of copolymerization system; proceeding technique route synthesis of main chain polymerization in the water solution. The getting big monomer possesses merits of high conversion rate, short reacting time, simple process flow and strong controlling property.
Description
Technical field
The present invention relates to the technical field of preparation concrete high-performance water reducer, be specifically related to a kind of concrete preparation method of graft copolymerization carboxylic acid series high-performance dehydragent.
Background technology
In recent years, along with domestic construction industry is flourish, the demand of concrete performance water reducer is increased year by year, China's building trade presses for the high-quality poly carboxylic acid series water reducer product that adapts to domestic construction market and technology of high performance concrete.
The building-up reactions of graft copolymerization carboxylic acid esters water reducer can be divided into two-step reaction: the first step reaction, generate polymerizable structural unit or " building block ", the reaction of second step, generate the co-poly carboxylic acid salt polymkeric substance of a fixed structure and molecular weight by condensation or polyaddition reaction, thereby have very strong dispersion water-reducing property.At present, producing poly carboxylic acid series water reducer both at home and abroad mainly obtains by two kinds of approach such as polymkeric substance grafting side chain and big monomer copolymerizations.
For example domestic disclosing among the patent CN1636922A on July 13rd, 2005 day, introduce two step synthesis techniques, as solvent, the vitriol oil is made catalyzer to the first step with toluene, and the polyoxyethylene glycol and the vinylformic acid of molecular weight 1000 is carried out esterification under temperature 90 ℃ ± 5 conditions, the polyoxyethylene glycol of molecular weight 1000 and vinylformic acid mol ratio are 1:1, used vinylformic acid dripped in 100 ± 10 minutes, and 5 ± 0.5 hours reaction times is after reaction finishes, extract water and toluene out, make the polyoxyethylene glycol mono acrylic ester.Second step, with the polyoxyethylene glycol mono acrylic ester that makes, with ammonium persulphate or Sodium Persulfate as initiator, mercaptoethanol is as chain-transfer agent, in the aqueous solution 85 ℃ ± 5 gather and, described vinylformic acid and initiator and chain-transfer agent dripped at 100 ± 10 minutes, the reaction times is 6 ± 0.5 hours, reaction finishes the back with sodium hydroxide PH=6.5 ± 0.5 that neutralizes, and obtains polycarboxylic acid series high efficiency water reducing agent.This method reaction times is longer, complex process, the difficult control of feed rate.
Report among the CN1316398A open day October 10 calendar year 2001, with the tosic acid is catalyzer, make methyl methacrylate and methyl Soxylat A 25-7 carry out transesterification reaction and introduce two keys, then in the reaction of second step, add methacrylic acid, be initiator, be that solvent gathers and reacts with the butanone with the dibenzoyl peroxide, after reaction finishes, need remove solvent under reduced pressure, obtain high efficiency water reducing agent.This water reducer is soluble in alkali, is insoluble in water, makes troubles to practice of construction.
Summary of the invention
The present invention proposes a kind of preparation technology of new poly carboxylic acid series water reducer, the problem that has solved the existence of the first esterification post polymerization of former employing two one step preparation methods effectively is low, the long reaction time of esterification rate of rotation, the dropping mode that adopts, feed rate should not be controlled, it is more loaded down with trivial details from purge process to exist intermediate section on the preparation method, cost is higher, with toluene as solvent, do not meet environmental requirement, not can be recycled, the mobile retentivity of the dressing polymkeric substance water-reducing rate that makes is poor, and is poor to the adaptive faculty of cement.The preparation method of graft copolymerization carboxylate high-performance dehydragent of the present invention, adopt full acid system esterification preparation earlier to have intermediate (big monomer) transformation efficiency height, the reaction times weak point of polymerization activity, exempted use nitrogen inert reaction atmosphere is provided, it is simple to have technical process, controllability is strong, keeps the safety in production and does not have the advantage of environmental pollution.Regulate the polymerization activity of copolymerization system by adding the 3rd monomer in the polyreaction, obtain even molecular weight distribution, particularly than under the low-dosage cement not of the same race being had adaptability preferably.
The invention provides a kind of preparation method of high-efficiency water-reducing agent of poly-carboxylic acid, it is characterized in that, may further comprise the steps:
The first step esterification: in reactor, add molecular weight M=1000～2000 methoxy poly (ethylene glycol)s, heated and stirred, temperature is controlled at 95 ℃～130 ℃, add hydroquinone of polymerization retarder or thiodiphenylamine, acrylic or methacrylic acid, the catalyzer vitriol oil and or tosic acid, band aqua hexanaphthene carries out esterification; After the isothermal reaction 3.5～5.5 hours, remove the band aqua, obtain macromer methoxyl-polyethyleneglycol methacrylic ester or methoxy poly (ethylene glycol) acrylate by vacuumizing; The mol ratio of methacrylic acid or vinylformic acid and methoxy poly (ethylene glycol) is 2～7.5:1 in the above-mentioned reaction; Hydroquinone of polymerization retarder or thiodiphenylamine consumption are 0.1%～5.0% of methacrylic acid or vinylformic acid quality; Catalyst levels is 1.0%～4.8% of a methoxy poly (ethylene glycol) quality; Band aqua hexanaphthene consumption is 15%～30% of a reactant total mass, and reactant refers to the used material outside the hexanaphthene in the reactor;
The second step polyreaction: the first step is reacted the big monomer that makes, add entry after the heating and melting, be warmed up to 50 ℃～65 ℃, fully after the stirring and dissolving, successively with chain-transfer agent sodium allyl sulfonate or Thiovanic acid, one of thiohydracrylic acid, regulating monomer acrylamide or butyl acrylate joins in the reaction vessel, it is 1%～15% aqueous solution that initiator ammonium persulfate or Potassium Persulphate are mixed with mass percent concentration, dividing three times adds, add for the first time initiator solution total mass 30%～50%, 75 ℃～90 ℃ of temperature of reaction, after the isothermal reaction 1 hour, add 30～50% of initiator solution total mass again, react after 1 hour, 15%～25% initiator solution that residue is accounted for total mass all adds, naturally cooling after 1～2.5 hour isothermal reaction time, when temperature is reduced to below 45 ℃, NaOH solution with mass percent concentration 30%～42%, quadrol, perhaps the trolamine organic amine obtains mass percent concentration 35%～45% graft copolymerization carboxylate high-performance dehydragent with resulting solution furnishing PH=7.5 ± 1.0; Wherein add initiator amount and big monomer mole ratio 0.15～0.84:1, acrylamide/butyl acrylate consumption and big monomer mole ratio 0.8～2.5:1, chain-transfer agent consumption and big monomer mole ratio 0.1～0.8:1.
Prioritization scheme in the esterification: hydroquinone of polymerization retarder or thiodiphenylamine consumption are 1.0%～3.0% of methacrylic acid or vinylformic acid quality; One of methacrylic acid, vinylformic acid are 2.5～5.0:1 with the mol ratio of methoxy poly (ethylene glycol); Described catalyst levels is 2.1%～3.8% of a methoxy poly (ethylene glycol) quality.
Beneficial effect of the present invention:
1. in the esterification, methacrylic acid or vinylformic acid adopt the method that once adds, and are about to that the first step esterification and second goes on foot in the polyreaction required methacrylic acid or vinylformic acid is disposable all joins in the first step esterification.According to a large amount of test-results, sour ether ratio improves can promote big monomeric speed of reaction, improves the reaction product esterification yield, and esterification yield reaches more than 95%, shortens the reaction times.The present invention has changed the method that traditional substep adds the carboxylic acid monomer, has significantly improved esterification yield, and has shortened the reaction times about 50%.
2. adopt the stable band aqua of a kind of nontoxic lower boiling; consumption by adjusting the band aqua both can control reaction temperature; promoting reacts completely carries out; can improve reaction atmosphere (inert band aqua exhausted air) again; two keys in the protection vinylformic acid can be not oxidized, avoided the complex operations of inflated with nitrogen exhausted air.The band aqua that reclaims is handled by molecular sieve, can recycle.Adopt molecular sieve to handle the band aqua, do not appear in the newspapers both at home and abroad.
3. in the polyreaction, chain-transfer agent, adjusting monomer adopt and once feed intake, and the fed batch method is adopted in the initiator agent, and simple to operate, controllability is strong.Polyreaction adopts the water-soluble medium polymerization, has so both helped the enforcement of suitability for industrialized production, can guarantee the safety and the cleaning of production process again.
4. synthetic water reducer has good adaptability to the cement in the different places of production, at the solid volume 0.2% of folding, during water cement ratio w/c=0.29, cement paste through the time loss in 2 hours very little.
5. this water reducer can be used for preparing high-strength concrete, pump concrete, self-leveling concrete, also can be used for the dispersion agent of coal water slurry and the friction reducer of oil well cement.
Description of drawings
Fig. 1 .GPC measures big monomeric molecular weight and distribution plan thereof
Fig. 2 .GPC measures synthetic water reducer molecular weight and distribution plan thereof
Embodiment
Embodiment 1
The methoxy poly (ethylene glycol) 80g that in the reaction vessel that stirring, condensation, effluent recycling device are housed, adds molecular weight M1000, fully melt, temperature is at 95 ℃, add hydroquinone of polymerization retarder 0.14g, react after 15 minutes, more in turn with vinylformic acid 14.4g, vitriol oil 1.98g, hexanaphthene 14.4g join in the reaction vessel, constant temperature 4 hours, esterification yield reaches 97.6%, removes hexanaphthene and obtains methoxy poly (ethylene glycol) acrylate (big monomer) by vacuumizing.The band aqua that reclaims is handled through the 3A molecular sieve again, can be recycled.In the second step polymerization process, in four neck flasks, add esterification and make all big monomer, water 55.19g continuously stirring, heating in water bath is warming up to 50 ℃.Successively with Thiovanic acid 1.26g, acrylamide 4.54g, the aqueous solution 46g of the ammonium persulphate mass percent concentration 15% of preparation joins in the reactor, be warmed up to 75 ℃ of temperature of reaction, isothermal reaction adds 15% ammonium persulfate aqueous solution 40.8g after 1 hour, react to add remaining 15% ammonium persulfate solution 15.33g after 1 hour again, and isothermal reaction is after 1.5 hours, naturally cool to 42 ℃, add 30% NaOH regulator solution pH=7.Make polycarboxylate water-reducer product 1, concentration 45.2%.
Embodiment 2
The methoxy poly (ethylene glycol) 90g that in the reaction vessel that stirring, condensation, effluent recycling device are housed, adds molecular weight M1300, fully melt, temperature is at 120 ℃, add stopper thiodiphenylamine 0.89g, react after 15 minutes, again in turn with methacrylic acid 29.76g, the vitriol oil and tosic acid 4.55g, hexanaphthene 37g, join in the reaction vessel, after 3.5 hours isothermal reaction time, esterification yield reaches 96.6%, removes hexanaphthene by vacuumizing, and obtains methoxy polyethylene glycol methacrylate-styrene polymer (big monomer).The band aqua that reclaims is handled through the 3A molecular sieve again, can recycle when producing next time.In the second step polymerization process, in four neck flasks, add esterification and make all big monomer, water 27.17g, continuously stirring, heating in water bath is warming up to 60 ℃, successively with thiohydracrylic acid 5.87g, the aqueous solution 118.5g of the ammonium persulphate mass percent concentration 1% of butyl acrylate 8.86g and preparation joins in the reactor, be warmed up to 85 ℃ of temperature of reaction, isothermal reaction adds 1% ammonium persulfate solution 71.1g after 1 hour, after reacting 1 hour again, add remaining 1% ammonium persulfate solution 47.4g, isothermal reaction control is after 1 hour, naturally cool to 45 ℃, add 42% trolamine regulator solution to pH=7.5.The polycarboxylate water-reducer product 2 that makes, concentration 35.2%.
Embodiment 3
The methoxy poly (ethylene glycol) 100g that in the reaction vessel that stirring, condensation, effluent recycling device are housed, adds molecular weight M1000, fully melt, temperature adds hydroquinone of polymerization retarder 0.014g at 130 ℃, react after 15 minutes, in turn with vinylformic acid 14.40g, tosic acid 1.14g, hexanaphthene 23g join in the reaction vessel again, after the isothermal reaction 4.5 hours, esterification yield reaches 97.2%, removes hexanaphthene by vacuumizing, and obtains methoxy poly (ethylene glycol) acrylate (big monomer).The band aqua that reclaims is handled through the 3A molecular sieve again, can be recycled.In the second step polymerization process, in four neck flasks, add esterification and make all big monomer, water 150.52g continuously stirring, heating in water bath is warming up to 65 ℃.Successively with sodium allyl sulfonate 7.9g, the aqueous solution 32.4g of the Potassium Persulphate mass percent concentration 10% of butyl acrylate 19.2g preparation joins in the reactor, be warmed up to 90 ℃ of temperature of reaction, isothermal reaction adds 10% persulfate aqueous solution 28.35g after 1 hour, react again and add remaining 10% potassium persulfate solution 20.25g after 1 hour, after the isothermal reaction 2 hours, naturally cool to 44 ℃, add 40% quadrol regulator solution to pH=7.The polycarboxylate water-reducer product 3 of system, concentration 39.88%.
Embodiment 4
The methoxy poly (ethylene glycol) 80g that in the reaction vessel that stirring, condensation, effluent recycling device are housed, adds molecular weight M2000, fully melt, temperature is at 120 ℃, add hydroquinone of polymerization retarder 1.29g, react after 15 minutes, again in turn with methacrylic acid 25.8g, tosic acid 5.08g, hexanaphthene 24g, join in the reaction vessel, isothermal reaction is after 5.5 hours, and esterification yield reaches 96.5%, remove hexanaphthene by vacuumizing, obtain methoxy polyethylene glycol methacrylate-styrene polymer (big monomer).The band aqua that reclaims is handled through molecular sieve again, can be recycled.In the second step polymerization process, in four neck flasks, add esterification and make all big monomer, water 69.87g continuously stirring, heating in water bath is warming up to 57 ℃.Successively with Thiovanic acid 1.47g, the aqueous solution 25.92g of the Potassium Persulphate mass percent concentration 5% of acrylamide 7.1g and preparation joins in the reactor, be warmed up to 85 ℃ of temperature of reaction, isothermal reaction adds 5% persulfate aqueous solution 43.24g after 1 hour, after reacting 1 hour again, add remaining 5% ammonium persulfate solution 17.28g, isothermal reaction naturally cools to 44 ℃ after 3.5 hours, adds the 45%NaOH regulator solution to pH=7.Make polycarboxylate water-reducer product 4, concentration 45.2%.
Implementation result
Flowing degree of net paste of cement
For water reducer relatively to the plastification effect of different cement, test determination with the clean slurry degree of mobilization of following several water reducers under the volume to different cement types.Test is undertaken by GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, and volume is the solid volume of folding.Test-results sees Table 1
Table 1 is mixed the flowing degree of net paste of cement of different PC water reducers
By data in the table as can be seen, under low-dosage, present method synthetic water reducer has adaptability preferably to different cement.
The concrete data
Table 2～4th, the preparation of synthetic polycarboxylic acid series high efficiency water reducing agent is used for the test-results of pumping C50 mix proportion and serviceability and mechanical property.Used two kinds of cement in the test, after various polycarboxylic acid series high efficiency water reducing agents added, various polycarboxylic acid series high efficiency water reducing agents added the back mechanical properties of concrete and all satisfy the C50 requirement, and bigger surplus capacity is arranged.
Table 2 is mixed the pumping C50 concrete mix of polycarboxylate water-reducer
Table 3 is mixed the pumping C50 workability of concrete energy of polycarboxylate water-reducer
Table 4 is mixed the pumping C50 mechanical properties of concrete of polycarboxylate water-reducer
The corresponding GPC of table 2. Fig. 1 measures big monomeric molecular weight GPC result
The corresponding GPC of table 3. Fig. 2 measures the molecular weight GPC result of synthetic water reducer
10
M
n M
w Mp Mz M
z+1 Mv Poly
The all sticking equal disper of the equal Z+1 of number average weight average peak position Z
Divide sity
The many branches of sub-quantum quantum quantum quantum quantum amount
(Dao Er (Dao Er (Dao Er (Dao Er (road (loosing property of Dao Er
)))) Er Dun))
1089 1105 1186 1082 1115 1157 1.01
987
Diminishing preface M
nM
wMp Mz M
Z+1M
vPolydi
The all sticking equal spersity of the agent number equal Z+1 of number weight average peak position z
Divide equally the branch branch and divide many branches
The sub-quantum quantum quantum quantum amount property of loosing
Amount (road (Dao Er (Dao Er (Dao Er (road (Dao Er
Er Dun) pause)) Er Dun))
)
Pc-1 1 854 2344 1526 5110 92981 2344 2.745
0 7 2 0 7 56
2 978 980 983 985 980 1.002
57
Claims (4)
1, a kind of preparation method of graft copolymerization carboxylate high-performance dehydragent is characterized in that,
May further comprise the steps:
The first step esterification: in reactor, add molecular weight M=1000～2000 methoxy poly (ethylene glycol)s, heated and stirred, temperature is controlled at 95 ℃～130 ℃, add hydroquinone of polymerization retarder or thiodiphenylamine, acrylic or methacrylic acid, the catalyzer vitriol oil and/or tosic acid, band aqua hexanaphthene carries out esterification; After the isothermal reaction 3.5～5.5 hours, remove the band aqua, obtain macromer methoxyl-polyethyleneglycol methacrylic ester or methoxy poly (ethylene glycol) acrylate by vacuumizing; The mol ratio of methacrylic acid or vinylformic acid and methoxy poly (ethylene glycol) is 2～7.5:1 in the above-mentioned reaction; Hydroquinone of polymerization retarder or thiodiphenylamine consumption are 0.1%～5.0% of methacrylic acid or vinylformic acid quality; Catalyst levels is 1.0%～4.8% of a methoxy poly (ethylene glycol) quality; Band aqua hexanaphthene consumption is 15%～30% of a reactant total mass, and reactant refers to the used material outside the hexanaphthene in the reactor;
The second step polyreaction: the first step is reacted the big monomer that makes, add entry after the heating and melting, be warmed up to 50 ℃～65 ℃, fully after the stirring and dissolving, successively with chain-transfer agent sodium allyl sulfonate or Thiovanic acid, one of thiohydracrylic acid, regulating monomer acrylamide or butyl acrylate joins in the reaction vessel, it is 1%～15% aqueous solution that initiator ammonium persulfate or Potassium Persulphate are mixed with mass percent concentration, dividing three times adds, add for the first time initiator solution total mass 30%～50%, 75 ℃～90 ℃ of temperature of reaction, after the isothermal reaction 1 hour, add 30～50% of initiator solution total mass again, react after 1 hour, 15%～25% initiator solution that residue is accounted for the initiator solution total mass all adds, naturally cooling after 1～2.5 hour isothermal reaction time, when temperature is reduced to below 45 ℃, NaOH solution with mass percent concentration 30%～42%, quadrol, perhaps the trolamine organic amine obtains mass percent concentration 35%～45% graft copolymerization carboxylate high-performance dehydragent with resulting solution furnishing PH=7.5 ± 1.0; Wherein adding initiator amount is 0.15～0.84:1 with big monomer mole ratio, and acrylamide or butyl acrylate consumption are 0.8～2.5:1 with big monomer mole ratio, and the chain-transfer agent consumption is 0.1～0.8:1 with big monomer mole ratio.
2. the preparation method of water reducer according to claim 1 is characterized in that, one of described methacrylic acid, vinylformic acid are 2.5～5.0:1 with the mol ratio of methoxy poly (ethylene glycol).
3. the preparation method of water reducer according to claim 1 is characterized in that, described stopper is 1.0%～3.0% of methacrylic acid or a vinylformic acid quality.
4. the preparation method of water reducer according to claim 1 is characterized in that, described catalyst levels is 2.1%～3.8% of a methoxy poly (ethylene glycol) quality.
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